Catalyst



Patented Apr. 27, 1948 a UNITED STATES PATENT OFFICE Robert I. stlrton, Bedondo Beach, cent, as-

slgnortoUnionOil Company of California, Angeles, Call! a corporation of No Drawing. ofltlnal application May 3, 1944,

Serial No. 533,949. DIM Ill all application February 12, 1948, Serial No. 647,215

8 Claims. (Cl. 25H) 1 This invention relates to catalysts and catalytic The catalytic treatment of hydrocarbons has processes for the processing of various hydrocar-, come to involve many varied and unrelated procbons and/or hydrocarbon mixtures. The invenesses which for purposes of this disclosure are tion also relates to a methodfor preparing the divided into two groups. Catalytic conversion catalysts. This application is a division of my 5 of hydrocarbonsisconsidered to include aromaticopending application Serial Number 533,949. zation, cracking, dehydrogenation. reforming of More particularly, the invention relates to the hydrocarbons, and any such process whereby a catalytic treatment oi! hydrocarbon stocks, such certain decree o dest uction of t e y o bon as catalytic dehydrogenation of light or normally t ls is mpli while Catalytic hy r gaseous hydrocarbons, such as propane, propene. lo enating is intended to include desulfurization, butane, butene, isobutane, isobutene, and the like, y il o nd y Such Process consisting of and the catalytic dehydrogenation of normally replacement of or addition to the hydrocarbon liquid hydrocarbons, such as pentane, pentene, molecule- These W groups. namely. c t i isopentane, isopentene, hexane, hexane, and, the r i n nd catalytic hydrogenating f hydr like, and catalytic reforming or aromatization 01 ns are bot cl n t broad onc p commercial naphthas and stocks boiling within of ta y ic treatment and will be used herein-- the gasoline range to produce improved motor after to t gu the two classes of reactions. fuels and also to produce aromatic hydrocarbons For the conversion and y sen ins of ysuch as benzene, toluene, xylenes, naphthalene dIOCM'bOB-S many catalytic agents have been 8 and substituted naphthalenes, and the like, The Ployed t y g de es of 81100858- 511011 invention further relates to the catalytic desuliurp a nts include the oiiides or other comization of petroleum fractions and/or combinaounds or meta s. suc as o i o ybdetions of said fractions. such as pressure distillate nickel- Zlnclead. beryllium, and even crude oils. c dmium, vanadium. 'mansanese', tantal m. tung- The principal objects of the invention are to Stan, titanium, plat um. eolumblum. scend ilm, provide a catalyst which is comparatively e sy to thoriumu Zirconium. in. P- produce, is not easily poisoned, has a long cata- D r, etc.. 0! c fl s 01 o 1' e 01 Such lytic life, is heat stable, and the particles of which compounds- All $11988 metals except beryllium are capable of retaining their mechanical strength and elnmlnum are vy m M ny of the during use and. which at the same time causes c ns ts a e tive only e s pport d high conversions to the desired products, which on carriers. such s the oxides of alumina. sproducts are determined by the nature of the feed nesiumr smconzil'mnmmi utaniumthorium, stocks em loyed and the particlflar condition of The oxideriof chromium d o ybdenum processing to which these feed stocks are subdistended onalumma are Preferred catalysts jggtei the above defined conversion processes.

A more specific object of the invention is to For example in a Process genera-11y described provide a catalyst carrier or support containas dehydrogenation; t lyst omposed of 5% ing a material which improves the stability of chmm1l1m0X1dBand95% l mina which has been catalysts employing this carrier. A further obactivated s p le of ffecting as much as about ject of the invention is to provide a catalyst car-- 40 28% conversion 01' normal butane to butenes at rier of such composition that the catalyst par-ti a temperatureoi about 1050 F., at substantially cles originally possess adequate mechanical atmosphe ic pressure a with 11 space v y of strength and that the catalyst retains its mefrom 15 to, volumes of fe d per volume of catchanical strength during use. Another object of 7 D m te- A18 in ai'omatization operathe invention to provide a catalyst carrier contiOhS a typical lly P p ta yst taining a materlalwhich improves the activity consisting of about 10% moly n QXide an of catalyst compositions employing said carrier. %u-lum1na w ich has been activated is capa l Other objects, features and advantages of the a ing the aromatic content of a n p invention will become apparent to those skilled boiling in the range of. about 200 F. to 250 F, in the art as the" description thereof proceeds. from about 14% to about 6 by volume at a 3 temperature of about 950 F. at a liquid hourly space velocity of about 1, and gauge pressure of about 100 pounds per square inch with 3000 cubic feet of added hydrogen per barrel of feed.

The above bed catalysts while possessing moderately hig initial activity and relatively high mechanical strength have undesirably short active lives and gradually lose their mechanical strength during continued operation and for these reasons must be discarded after relatively short periods of use, It is thought that the decrease in activity and shortness oflife of a catalyst are related to a loss in mechanical strength but the reason for this loss and methods for preventing it are not thoroughly understood and are not to be construed as limiting my' invention. It has been considered. however, that this loss in mechanical strengthisduetothelackorheatstability of the catalyst and may occur during the useofacatalysteitherinthecatalyzingstage or more probably to greaterdegree in the meneration stage of the operation, during which stage the temperatures attained within the catalyst bed listed above and preferably a compound of which has been activated have been found to be are often considerably higher than those used in the catalyzing stage.

The method. of. testing the heat stability of a catalyst which has been accepted by the industry as a means of predicting the relative catalytic life of a catalyst consists in the calcining oi a catalyst at elevated temperatures such as about 1i'l0 F. or higher for a few hours. Many catalysts of the type described above are known to lose mechanical strength and catalytic activity after they have been subjected to such a process. It has been found that this loss in catalytic activity is in close agreement with the loss in mechanical strength and it has also been found that those catalysts which retain their mechanical strength upon calcination at elevated temperatures will also retain their catalyticactivity.

\ More important it has been shown that those catalysts which lose mechanical strength and catalyst activity upon calcination at elevated temperatures will have comparatively short catalytic life and will break down in the reactor bed with consequent production of large quantities of fines which are detrimetai to the proper functioning of the bed, necessitating too frequent replacement of the catalyst. Conversely, those catalysts which are found to retain their mechanical strength in the calcining test are found not only to have long catalytic life but do not break down into fines during the normal use in the catalytic process. For example, a fresh sample of the commercially prepared catalyst, referred to above,

after calcining at 1470 F. becomes very soft and powders easily by rubbing between the fingers and at the same time a relatively large proportion of the activity of this catalyst has been destroyed as shown by its ability to increase the aromatic content of the aforementioned naphtha fraction to only about 17% by volume as com-' pared to an effected increase to 6.0% by volume when fresh.

My invention relates to an improvement in catalytic compositions for use in the above processes for hydrocarbon conversion and hydrogenating. Specifically, my invention relates to improvement in a carrier composition used in the preparation of catalysts for these processes. I have discovered that the inclusion of relatively small amoimts of the compound consisting of an aluminum salt of pentavalent phosphous in the desired catalyst carrier, such carrier having distended thereon a compound of a heavy metal as excellent carriers on which may be distended 1 to by weight or preferably about 11% by weight of molybdenum oxide. Preferably the mount of aluminum ortho phosphate should be about 6%, although it may be decreased to as low at 2% or increased to about 10% without substantially changing the performance of the'cataiyst. The preferred amount of molybdenum oxide is about 11%. I have found, however, that it may vary within the limits of from about 7% to 13% with good results. Thus, while the final composition of the preferred reforming catalyst will contain about 83% by weight of alumina, 6% by weight of aluminum ortho phosphate and about 11% by weight of molybdenum oxide, catalyst compositions containing about 79% to 93% by weight of alumina, about 2% to 8% by weight of aluminum ortho phosphate and about 5% to 13% by weight of an oxide, such as chromium or molybdenum or the like are excellent catalysts. Moreover, catalysts comprising about 70% to 98% by weight of alumina, about 1% to 15% by weight of aluminum ortho phosphate and about 1% to 15% by weight of an oxide of a metal selected from the left-hand column of the sixth group of the periodic table conform to the compositions indicated above for active heat stable and mechanically strong reforming catalysts and are desirable catalysts conforming to the intent of my invention.

In like manner whereas my preferred catalysts for the hydrogenating of hydrocarbons comprises about 60% by weight of alumnia, 6% by weight of aluminum ortho phosphate, and about 34% by weight of cobalt molybdate, catalyst compositions containing from 35% to 94% by weight of alumine, 1% to 15% by weight of aluminum ortho phosphate and from 5% to 50% by weight of cobalt molybdate are excellent catalysts. Moreover, catalysts comprising approximately 50% to 95% by weight of alumina, 1% to 15% by weight of aluminum ortho phosphate and 1% to 49% by weight of an active hydrogenating agent such as the oxides of the metals selected from the fourth series of the eighth group of the periodic table are excellent catalysts for hydrocarbon hydrogenating.

It is also within the spirit of this invention to employ this improved support material as a catalyst without the addition of the aforementioned catalytic agents. In such cases it may be necessary to increase the proportion of the aluminum,

Concentrated ammonium hydroxide (285% superior catalyst for the catalytic treatment of hydrocarbon fractions.

The invention may perhaps by reference to the following example which should be consihered as being only illustrative of the invention and is not to be taken as in any way limiting my invention:

A catalyst composed of alumina, aluminum ortho phosphate and molybdenum oxide was preared as follows:

-A quantity of 5125 grams of commercial aluminum gel of the following composition:

' which exhibited a pH of 1c and a specific gravity of 1.05 was added to five liters of distilled water in a stainless steel vessel. After thorough mixing, the pH was determined and found to be 10.3. One hundred and twenty six grams of aluminum nitrate (A1(NO3)3.9H20) was dissolved in one liter of distilled water and added to the stirred gel suspension, the resulting mixture having a pH of 4.3. To this mixture was added a solution of 45 grams of monohydrogen ammonium ortho phosphate in one liter of distilled water. Th suspension was agitated for 30 minutes and allowed to stand undisturbed thereafter for 48 hours. The mixture was then filtered and the cake washed twice by resuspension in liters of distilled water and finally washed on the filter with 2 liters of distilled water. The gel cake was then cut into cubes approximately 1 inch square and dried in air at 100-120 C. for 30 hours and at 160 C. for 48 hours and was lastly calcined for two hours at 500 C. and crushed and screened to 4-8 mesh granules. I g

Two hundred and six grams of the aforesaid support was immersed in a solution of the following composition:

Grams Distilled water 201 Ammonium molybdate- (82.5% M00 4'7 N'Ha) 16 and agitated therein for a period of approximately 4 minutes. This material was then filtered with suction and the impregnated gel was then dried at 100 C. to 120 C. for 36 hours and subsequently at 600 C. for two hours. This completed catalyst hereinafter referred to as catalyst No. 1 showed on analysis a composition of approximately 82.92 weight per cent alumina, 6.75 weight per cent aluminum ortho phosphate, and approximately 10.33 weight per cent molybdenum oxide. Another catalyst sample hereinafter referred to as catalyst No. 2 was prepared in the same manneras catalyst No. 1 above, using the same steps and procedures without adding the aluminum nitrate and mono-hydrogen ammonium ortho phosphate, giving a catalyst preparation composed of about 90.5 weight per cent alumina and about 9.5 per cent by weight of molybdenum oxide. v r

Portions of these catalysts as completed, and after calcining in air at about l4 72 F. for 6 hours, were then used in aromatizing a petroleum naphbe best understood the boiling in the range of about 200 F. to 280 F. and containing about 14.3% by volume of aromatics. The conditions used inthe aromatization operations were the same in every case and were about the following: liquid hourly space velocity, 1; isothermal block temperature, 950 F. pounds per square inch gauge pressure; 3000 cubic feet of added hydrogen per barrel of feed; and a 4 hour'process period.

The difference in the activity and heat stability of these two catalysts, brought about by the presence in catalyst No. 1 of 6.75 weight per cent aluminum ortho phosphate, can best be appreciated by reference to the brief tabulation of the slate obtained from the above described operaons:

Table 1 Catalyst No V l 1 2 2 Calcination temperature, F..- Fresh Fresh 1,47 Liq. recovery, vol. per cent of feed. 76. 2 77. 0 77. 2 l 82. 8 Aromatics, vol. per cent of iced 46. 2 48. 2 42. 9 43. 0 Synthetic aromatics, vol. per cent of feed 31.9 34 0 28.6 28 7 It is seen from these data that a decided improvement in initial activity as well as in activity of the calcined catalysts is brought about by the Iprresiance of aluminum ortho phosphate in catalyst Exsuru: 2

- highly adsorptive gel of the above composition.

This product, crushed and screened to 8 to 20 mesh, was then impregnated with a solution of chromium salt as follows: To 400 grams of the ignited carrier was added 33 grams of ammonium dichromate ((NHO 2Crz0v) dissolved in 300 ml. of distilled water, and this mixture was heated to dryness with agitation, dried and ignited as above to obtain a finished catalyst containing about 5% by weight of Crz0:,,1.1% by weight of aluminum ortho phosphate and the remainder alumina.

The above catalyst hereinafter referred to as catalyst No. 3 was employed to dehydrogenate butane in the following operation: Gaseous nbutane was preheated and passed at a rat of 5 liters per hour through 5 ml. of catalyst ina reaction chamber at atemperature of about 565 0., (1050 F.), and substantially atmospheric pressure. This feed rate corresponds to a space velocity (volumes of gaseous feed,,measured at 0 C. and I60 mm. of pressure, per volume of catalyst per hour) of 912. Under these conditions employing catalyst No. 3 the average conversion of butane to butenes over a 2-hour reaction period was 32.1% (mol. per cent). Substantially the same conversions were obtained after regeneration of the above catalyst.

Employing the heat stability test as described above, a sample of this catalyst was calcined at- 850 C. (1562 F.) for six hours in air. At the phate is omitted from its composition. With the aluminum ortho phosphate incorporated. however, catalyst No. 3 upon calcination at 850 C. retained essentially all of its original form and mechanical strength, and gave a 24% conversion of butane to butenes when tested as above.

Enron 3 A catalyst for the desuli'urization of hydrocarbon stocks was prepared as follows: To 73' pounds of aqueous alumina gel (about AhOi) suspended in 40 liters of. distilled water was added with constant stirring a solution of 808 grams or Baker's C. P. aluminum nitrate (A1(NO:):.9H:O) in 6 liters of distilled water, the resulting mixture having a pH 01' 4.3. To this mixture was added a solution of 290 grams of mono-hydrogen ammonium ortho phosphate in 6 liters of distilled water. The solution was agitated for 30 minutes and allowed to stand overnight. To this suspension of alumina and aluminum ortho phosphate was added a solution or 2350 grams of Baker's C. P. cobalt nitrate (Co(NOs):.6H:O) in 10 liters oil-distilled water.

This addition was made slowly over a period of approximately 2 hours accompanied by vigorous agitation of the suspension. A solution was prepared comprising 1425 grams of ammonium molybdate ((NHdcM01024AH2O) dissolved in 10 liters of distilled water containing 1.06 liters of 28.5% NH: solution. This ammonium molybdate solution was added to the above mixture over a period of 2 hours, constant agitation being maintained throughout the addition. After continued stirring for 2 hours the suspension of completed catalyst had a pH of 7.4. The material was filtered and water-washed three times by resuspension in 40 liters of distilled water, out into 1 inch cubes and dried at 100 C. for four days. Alter drying at 190 C. for 24 hours and at 600 C. for 2 hours a hard, adsorbent, gel

type solid resulted which will hereinafter be referred to as catalyst No. 4 and which had approximately the following composition:

Wt. per- Another desulfurization catalyst hereinafter referred to as catalyst No. 5 was prepared in the same manner without the addition of aluminum ortho phosphate and had approximately the following composition:

Component 2,2 3

Alumina 65.0 Cobalt molybdate 35. 0

Catalysts No. 4 and 5 were then used when fresh and after calcination at 800 C. (1472 F.) for desulfurizing a Santa Maria pressure distillate boiling in the range of 100-400' F. and containing approximately 3.5% by weight of sulfur.

Operating conditions for these four runs were the same in every case and were about the fol-- lowing: liquid hourly space velocity, 1; isothermal block temperature, 700' I"; 250 pounds per square inch gauge pressure, 3000 cubic feet of added hydrogen per barrel of feed: and a 12 hour process period. Pertinent data from these runs are tabulatedin'lable2below:

It is apparent from these data that whereas the initial activities of the fresh catalysts are essentially the same, the activity of the calcined catalystNo. 4 is considerably higher than that of the calcined catalyst No. 5 due to the presence therein of 3.5 weight per cent aluminum ortho phosphate. It would be reasonable to presume, therefore, based on heat stability 01' these materials that catalyst No. 4 containing aluminum ortho phosphate would give a longer efiective catalyst life than catalyst No, 5 which does not contain thealuminum ortho phosphate.

While the catalysts described in the above examples are of the aromatizing, dehydrogenating, and desuliurizing type and are composed of alumina and a catalytic agent as the catalyst and aluminum ortho phosphate as the stabilizer, it is within the spirit of the invention to use aluminum ortho phosphate as the stabilizer for other arcmatizing or reforming catalysts and also in catalysts employed in hydrogenating processes other than desulfurization, such as hydrogenation. I prefer to employ those reforming catalysts which use as carriers such solid adsorbent materials as alumina, magnesia, and

' the like, and upon which are distened the oxides of the metals of the left-hand column of the sixth group of the periodic table. In like manner, I prefer to employ those hydrogenating catalysts which use as supports such solid adsorbent materials as alumina, magnesia, and the like, and upon which distended the oxides of the metals of the fourth series of the eighth group of the periodic table or the combines oxides of the metals of the fourth series of the eighth group of the periodic table with the metals of the left-hand column of the sixth group. of the periodic table.

Moreover, the aromatization operations described in the above examples are only illustrative of the possible uses of catalysts stabilized by the addition thereto of an aluminum salt of pentavalent phosphorus and it is within the scope of the invention to use any or all of the above types of catalysts in carrying out the reforming processes defined as dehydrogenation, cracking.

aromitization and the like as well as the hydro-' a -14.5 pounds up to about 1000 pounds per square inch using catalysts having the compositions disclosed above.

amass in like manner any or all of the above-named processes for the hydrogenating of hy bons may be carried out at temperatures in the range of about 400 1''. to about 1000' F. and under gauge pressures of about atmospheric to about 1000 pounds per square inch using catalysts having the compositions described above.

The foregoing description of my invention is notv to be considered as limiting since many variations may occur to those skilled in the art without departing from the scope of the claims or the spirit thereof.

Iclaim:

1. A catalyst consisting essentially of a major proportion of a carrier selected from the class consisting of alumina-which has been activated and esia, and .a minor proportion between about 1% and 15% ot a heavy metal oxide catalytic agent distended thereon. said carrier having been stabilized by the addition thereto between 1% and 15% of aluminum orthophosphate. 2. A catalyst consisting essentially of a major proportion of a stabilized carrier and a minor proportion between about 1% and 15% of a heavy metal oxide catalytic agent distended thereon,

- l0 ortbophospbate. and oxide of a metal or the left-hand column of group VI, and constitutes between 1% and 15% of the and 15% oi aluminum orthophosphate.

8. A catalyst consisting essentially of a mador proportion of a stabilized carrier and a minor proportion of cobalt molybdate distended thereon,

said carrier consisting essentially of precipitated alumina on which has been precipitated between about 1% and 15% of aluminum orthophosphate.

said stabilized carrier consisting essentially of alumina which has been activated and which has been stabilized by the addition thereto of between about 1% and 15% of aluminum orthophosphate.

3. A catalyst consisting essentially of a major proportion of a stabilized carrier and a minor proportion of a catalytic agent distended thereon, in which catalyst the stabilized carrier consists essentially of alumina which has been activated and which has been stabilized by the addition thereto I of between about 1% and 15% of aluminum ROBERT I. S'I'IRTON.

REFERENCES CITED The following referencu are of record in the tile of this patent:

Number Name Date 1,271,013 Bosch et al July 2, 1918 2,007,116 Walker July 2, 1935 2,118,001 Andrews et a1. -May 17, 1938 2,181,840 Deanesley et al Nov. 28, 1939 2,325,033 Byrns July 27, 1943 2,349,827

Mattox May 30, 1944 the catalytic agent is an 

